Amino-functionalized polysulfone as well as efficient preparation method and application thereof

Abstract

The invention relates to amino-functionalized polysulfone as well as an efficient preparation method and application thereof. The invention belongs to the field of functionalized polysulfone preparation. The invention aims to solve the technical problems of high cost, tedious steps and low synthesis efficiency of the existing method for preparing amino-functionalized polysulfone. The amino-functionalized polysulfone polymer is synthesized and prepared by selecting a specific active monomer, so that the steps of protecting and deprotecting the amino group on the monomer are not needed in the polymerization process, and the conjugated structure in the specific dichloro monomer can stabilize the amino group and obviously improve the polymerization reaction efficiency. The preparation method has the advantages of simple process, easily available raw materials and low cost. The material is applied to the fields of medical instruments, aerospace, electronics, food and daily necessities.

Description

Technical Field

[0001] The invention belongs to the field of functionalized polysulfone preparation, and specifically relates to amino-functionalized polysulfone and an efficient preparation method and application thereof. Background Art

[0002] Polysulfone is a sulfone group (-SO 2 -) and arylene thermoplastic resins have excellent mechanical properties and thermal stability, high strength, high rigidity, hydrolysis resistance, good dimensional stability and tolerance to general acids and alkalis. They are widely used in the production of medical devices, aerospace, electronic appliances, food and daily necessities. It is a high-performance engineering plastic with a wide range of applications.

[0003] However, the conventional polysulfone materials with non-functionalized main chains prepared by dehydration condensation of bisphenol A and dichlorodiphenyl sulfone have the following problems: (1) the polysulfone polymers with non-functionalized main chains have hydrophobic properties, which will cause serious membrane fouling problems when used in hemodialysis membranes, ultrafiltration membranes, and reverse osmosis bottom membranes, limiting the application of polysulfone materials; (2) the conventional polysulfone polymer main chains do not have sites available for functionalization, which imposes some restrictions on the functionalization of polysulfones, restricting their application in some special occasions.

[0004] Amino groups are hydrophilic functional groups with high reactivity. Introducing amine groups into the main chain of polymers can improve the hydrophilicity of polymers on the one hand; on the other hand, different functional modifications can be performed on polymers and post-processing steps such as grafting and cross-linking can be achieved, thereby realizing different functional applications in many fields such as petrochemicals, fine chemicals, and medical production. Currently, the existing methods usually prepare amino-functionalized polymers by selecting or synthesizing bisphenol monomers with amino groups for dehydration condensation. The amino-active monomers selected are mostly bisphenol monomers. However, due to the high reactivity of the amino group, most of the amino monomers are cross-linked during the polymerization process. Therefore, special reaction steps of protecting the amino monomers before the polymerization reaction and deprotecting after the polymerization reaction are often required, and the selected bisphenol monomers are relatively expensive. In addition, the reactivity of the amino-modified bisphenol monomers is not high, resulting in a low synthesis efficiency of amino-functionalized polysulfones. It is urgent to develop a new method for efficiently synthesizing amino-functionalized polysulfones. Summary of the invention

[0005] The purpose of the present invention is to solve the technical problems of the existing method for preparing amino-functionalized polysulfone, which is high cost, complicated steps and low synthesis efficiency, and to provide an amino-functionalized polysulfone and an efficient preparation method and application thereof.

[0006] The technical solution of the present invention is as follows:

[0007] One of the purposes of the present invention is to provide an amino-functionalized polysulfone having the general structural formula shown in formula (1):

[0008]

[0009] Where 0<x<1; It is one or more of the formulas (2) to (15):

[0010]

[0011] Preferably, When is one, the amino-functionalized polysulfone structure is one of formulas (16) to (29):

[0012]

[0013]

[0014]

[0015] Where 0<x<1.

[0016] The second object of the present invention is to provide an efficient preparation method of the above-mentioned amino-functionalized polysulfone, wherein the preparation method is carried out according to the following steps:

[0017] Under the protection of an inert atmosphere and the action of a base catalyst, one or more dichloro reactive monomers containing an amino group are subjected to a nucleophilic polycondensation reaction with a dihalogen diphenyl sulfone monomer and a bisphenol A monomer in a polar aprotic solvent to obtain an amino-functionalized polysulfone;

[0018] The amino-containing dichloro reactive monomer has a structure as shown in formulas (30) to (43):

[0019]

[0020] Preferably, in the above preparation method, the molar ratio of the amino-containing dichloro reactive monomer, the dihalodiphenyl sulfone monomer, the bisphenol A monomer and the base catalyst is y:(1-y):1:(1.05-2.5), wherein 0<y<1.

[0021] Preferably, in the above preparation method: the base catalyst is an alkali metal hydroxide and / or an alkali metal carbonate.

[0022] Preferably, in the above preparation method: the polar aprotic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and cyclopentane.

[0023] Preferably, in the above preparation method: a water-carrying agent is also included in the reaction process, and the water-carrying agent is toluene, xylene or cyclohexane.

[0024] Preferably, in the above preparation method, the nucleophilic polycondensation reaction temperature is 180-230°C, and the time is 1-7 hours. More preferably, the nucleophilic polycondensation reaction temperature is 200-230°C, and the time is 1-4 hours.

[0025] The third object of the present invention is to provide an application of the above amino-functionalized polysulfone in the fields of medical equipment, aerospace, electronic appliances, food and daily necessities.

[0026] Compared with the prior art, the present invention has the following significant effects:

[0027] (1) The present invention selects specific active monomers to synthesize and prepare amino-functionalized polysulfone polymers, thereby achieving the design purpose. The synthesized amino-functionalized polymer significantly improves the hydrophilicity of the polysulfone polymer by introducing side chain amino groups into the polymer main chain. At the same time, the introduction of active amino groups provides active sites for subsequent other functionalization treatments or post-treatment steps such as grafting and cross-linking, thereby broadening the application field of polysulfone polymers.

[0028] (2) The present invention introduces a dichloro monomer with a specific structure during the polymerization process. Not only does it not require the steps of protecting and deprotecting the amino group on the monomer during the polymerization process, but the conjugated structure in the specific dichloro monomer can stabilize the amino group, thereby significantly improving the polymerization reaction efficiency.

[0029] (3) The preparation method provided by the present invention has a simple process, the raw materials are easily available and the cost is low, and it has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the NMR spectrum of the amino-functionalized polysulfone prepared in Example 1. DETAILED DESCRIPTION

[0031] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the art unless otherwise specified, and can be obtained through commercial channels by those skilled in the art.

[0033] The terms "comprising," "including," "having," "containing," or any other variations thereof, as used in the following examples, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus comprising the listed elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

[0034] When equivalent, concentration or other value or parameter is represented by the range limited by range, preferred range or a series of upper preferred value and lower preferred value, this should be understood as specifically disclosing all ranges formed by any pairing of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the scope is disclosed separately. For example, when disclosing range "1 to 5", described range should be interpreted as including range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5" etc. When numerical range is described in this article, unless otherwise stated, the scope is intended to include its end value and all integers and fractions within the scope. In the present application specification and claims, range limitation can be combined and / or interchanged, if these ranges are not otherwise stated, include all sub-ranges contained therein.

[0035] The indefinite articles "a" and "an" before the elements or components of the present invention have no limitation on the quantity requirements (i.e. the number of occurrences) of the elements or components. Therefore, "a" or "an" should be interpreted as including one or at least one, and the elements or components in the singular form also include the plural form, unless the quantity obviously refers to the singular form only.

[0036] The "one embodiment" or "embodiment" of the present invention refers to a specific feature, structure or characteristic that can be included in at least one implementation of the present invention. The "in one embodiment" that appears in different places in this specification does not refer to the same embodiment, nor is it a separate or selective embodiment that is mutually exclusive with other embodiments.

[0037] The endpoints and any values ​​of the ranges disclosed in the invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article.

[0038] Example 1

[0039] 22.829g (0.1mol) of bisphenol A monomer, 22.973g (0.08mol) of dichlorodiphenyl sulfone monomer, 3.28g (0.02mol) of 2-amino-4,6-dichloropyrimidine represented by formula (30), 10.7309g (0.15mol) of anhydrous potassium carbonate, and 100mL of N-methylpyrrolidone were added to a 250mL three-necked flask containing a mechanical stirrer, a nitrogen inlet, a water separator, and a condenser. The mixture was heated to 220°C under nitrogen blowing conditions for 4h to obtain a reddish brown viscous polymer solution. After dilution with 100mL of N-methylpyrrolidone, the solution was centrifuged to remove potassium carbonate, and the obtained solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was crushed, washed, and dried to obtain an amino-functionalized polysulfone polymer. The structure is shown in the figure:

[0040]

[0041] Example 2

[0042] 22.829g (0.1mol) of bisphenol A monomer, 14.385g (0.05mol) of dichlorodiphenyl sulfone monomer, 8.199g (0.05mol) of 2-amino-4,6-dichloropyrimidine represented by formula (30) and 10.7309g (0.15mol) of anhydrous potassium carbonate, and 100mL of N-methylpyrrolidone were added to a 250mL three-necked flask containing a mechanical stirrer, a nitrogen inlet, a water separator and a condenser, and heated to 230°C under nitrogen blowing conditions for 2h to obtain a reddish brown viscous polymer solution, which was diluted by adding 100mL of N-methylpyrrolidone and centrifuged to remove potassium carbonate, and the obtained solution was poured into a dilute hydrochloric acid solution for phase inversion, and the obtained solid was crushed, washed and dried to obtain an amino-functionalized polysulfone polymer. The structure is shown in the figure:

[0043]

[0044] Example 3

[0045] 22.829g (0.1mol) of bisphenol A monomer, 14.385g (0.05mol) of dichlorodiphenyl sulfone monomer, 8.199g (0.05mol) of 4-amino-2,6-dichloropyrimidine represented by formula (31) and 10.7309g (0.15mol) of anhydrous potassium carbonate, 100mL of N-methylpyrrolidone were added to a 250mL three-necked flask with mechanical stirring, nitrogen inlet, water separator and condenser, heated to 180°C under nitrogen blowing conditions for 7h to obtain a reddish brown viscous polymer solution, added 100mL of N-methylpyrrolidone to dilute and centrifuged to remove potassium carbonate, the obtained solution was poured into a dilute hydrochloric acid solution for phase inversion, the obtained solid was crushed, washed and dried to obtain an amino-functionalized polysulfone polymer. The structure is shown in the figure:

[0046]

[0047] Embodiment 4:

[0048] 22.829g (0.1mol) of bisphenol A monomer, 14.385g (0.05mol) of dichlorodiphenyl sulfone monomer, 8.199g (0.05mol) of 5-amino-4,6-dichloropyrimidine represented by formula (32) and 10.7309g (0.15mol) of anhydrous potassium carbonate, 100mL of N-methylpyrrolidone were added to a 250mL three-necked flask with mechanical stirring, nitrogen inlet, water separator and condenser, heated to 200℃ under nitrogen blowing conditions for 4h to obtain a reddish brown viscous polymer solution, added 100mL of N-methylpyrrolidone to dilute and centrifuged to remove potassium carbonate, the obtained solution was poured into a dilute hydrochloric acid solution for phase inversion, the obtained solid was crushed, washed and dried to obtain an amino-functionalized polysulfone polymer. The structure is shown in the figure:

[0049]

[0050] Embodiment 5:

[0051] 22.829 g (0.1 mol) of bisphenol A monomer, 14.385 g (0.05 mol) of dichlorodiphenyl sulfone monomer, 8.199 g (0.025 mol) of 5-amino-4,6-dichloropyrimidine represented by formula (32), 8.199 g (0.025 mol) of 2-amino-4,6-dichloropyrimidine represented by formula (30) and 10.7309 g (0.15 mol) of anhydrous potassium carbonate and 100 mL of N-methylpyrrolidone were added to a 250 mL three-necked flask containing a mechanical stirrer, a nitrogen inlet, a water separator and a condenser. The mixture was heated to 230° C. under nitrogen blowing conditions and reacted for 2.5 h to obtain a reddish brown viscous polymer solution. 100 mL of N-methylpyrrolidone was added to dilute the solution and the solution was centrifuged to remove potassium carbonate. The obtained solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was crushed, washed and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is shown in the figure:

[0052]

[0053] The above are only preferred specific embodiments of the present invention, which are all different implementations based on the overall concept of the present invention, and the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. An amino-functionalized polysulfone, characterized in that Its general structural formula is shown in formula (1): Where 0<x<1; It is one or more of the formulas (2) to (15):

2. The polysulfone according to claim 1, characterized in that When is one, the amino-functionalized polysulfone structure is one of formulas (16) to (29): Where 0<x<1.

3. The efficient preparation method of polysulfone according to claim 1 or 2, characterized in that: The method: Under the protection of an inert atmosphere and the action of a base catalyst, one or more dichloro reactive monomers containing an amino group are subjected to a nucleophilic polycondensation reaction with a dihalogen diphenyl sulfone monomer and a bisphenol A monomer in a polar aprotic solvent to obtain an amino-functionalized polysulfone; The amino-containing dichloro reactive monomer has a structure as shown in formulas (30) to (43):

4. The method according to claim 3, characterized in that The molar ratio of the amino-containing dichloro reactive monomer, the dihalogen diphenyl sulfone monomer, the bisphenol A monomer and the base catalyst is y:(1-y):1:(1.05-2.5), wherein 0<y<1.

5. The method according to claim 3, characterized in that: The base catalyst is an alkali metal hydroxide and / or an alkali metal carbonate.

6. The method according to claim 3, characterized in that The polar aprotic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and cyclopentane.

7. The method according to claim 3, characterized in that The reaction process also includes a water-carrying agent.

8. The method according to claim 7, characterized in that The water-carrying agent is toluene, xylene or cyclohexane.

9. The method according to claim 3, characterized in that: The nucleophilic condensation reaction temperature is 180-230°C and the time is 1-7h.

10. Use of the polysulfone according to claim 1 or 2 in the fields of medical equipment, aerospace, electronic appliances, food and daily necessities.

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